JPH01149806A - Production of olefin polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer having high stereoregularity, suppressing the contamination with the residue of catalyst, by polymerizing an olefin in the presence of a catalyst derived from an organic Al compound, an electron donative compound and a solid catalyst component obtained by reacting 4 specific kinds of components. CONSTITUTION:An olefin is polymerized in the presence of a catalyst derived from (A) a solid catalyst component obtained by reacting (i) a dialkoxymagnesium, (ii) a mono and/or diester of an aromatic dicarboxylic acid (e.g., dibutyl phthalate), (iii) a silicon compound of formula Si(OR<1>)mX [R<1> is (cyclo)alkyl or aryl; X<1> is halogen; m is 0-3.0] (e.g., SiCl4) and (iv) a titanium tetrahalide, (B) an organic Al compound (e.g., trimethylaluminum) and (C) an electron donative compound (e.g., benzoic acid or acetone).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an olefin polymer, and more specifically, the present invention relates to a method for producing an olefin polymer, and more specifically, the present invention relates to a method for producing an olefin polymer. The present invention relates to a method for producing an olefin polymer having high stereoregularity.

[Prior art and its problems] Conventionally, olefin polymers are produced using a Ziegler-Natsuta catalyst that combines a solid catalyst component in which a titanium component is supported on a partially halogenated dialkoxymagnesium carrier. The method was known (Special Publication No. 60-25 of the Showa era)
Publication No. 441).

However, although the above-mentioned catalyst has a high polymerization activity per unit time at the initial stage of polymerization, it decreases significantly as the polymerization time passes. Therefore, when longer polymerization times are required, as in the case of block copolymerization reactions, the use of the above catalysts is disadvantageous in terms of production.

The present invention overcomes the above-mentioned conventional drawbacks, and produces an olefin polymer in which the polymerization activity of the catalyst is high, the decrease in polymerization activity over time is small, the stereoregularity of the obtained olefin polymer is high, and the contamination of catalyst residue is small. The purpose is to provide a manufacturing method for.

[Means for Solving the Problems] As a result of intensive research in order to achieve the above object, the present inventors found that olefins are The present inventors have discovered that the above-mentioned excellent effects can be obtained by polymerizing the above-described materials, and have completed the present invention.

That is, the composition of the present invention is as follows: a) dialkoxymagnesium; b) monoester of aromatic dicarboxylic acid and/or diester of aromatic dicarboxylic acid; and C) the following formula: 5i
(OR'), X'4-m C In the formula, R1 represents an alkyl group, a cycloalkyl group, or an aryl group,
represents a halogen atom such as chlorine or bromine, and m is 0 to 3.0
indicates a real number between . ) and (A) obtained by reacting a reaction product obtained by reacting with a silicon compound represented by d) titanium tetrahalide.
This is a method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of a catalyst obtained from a solid catalyst component, (B) an organoaluminum compound, and (C) an electron-donating compound.

About the catalyst As shown in FIG. 1, the catalyst of the present invention is a reaction product obtained by reacting dialkoxymagnesium with a monoester of an aromatic dicarboxylic acid and/or a diester of an aromatic dicarboxylic acid with a silicon compound. , a solid catalyst component obtained by reacting titanium tetrahalide (
A), an organoaluminum compound (B), and an electron-donating compound (C).

Regarding the solid catalyst component (A), examples of the dialkoxymagnesium include jetoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, dipropoxymagnesium, di-5ec-
Examples include butoxymagnesium, di-tert-butoxymagnesium, diisopropoxymagnesium, and the like.

In the present invention, one type of the above-mentioned various dialkoxymagnesiums may be used alone, or two or more types thereof may be used in combination.

Among the various dialkoxymagnesiums mentioned above, dialkoxymagnesiums having an alkoxy group having 1 to 4 carbon atoms are preferred, and jetoxymagnesium and dipropoxymagnesium are particularly preferred.

The mono-aromatic dicarboxylic acid and the diester of aromatic dicarboxylic acid are preferably monoesters of phthalic acid and diesters thereof, such as monomethyl phthalate, dimethyl phthalate, monomethyl terephthalate, dimethyl terephthalate, monoethyl phthalate,
Diethyl phthalate, monoethyl terephthalate, diethyl terephthalate, monopropyl phthalate, dipropyl phthalate, monopropyl terephthalate, dipropyl terephthalate, monobutyl phthalate, dibutyl phthalate, monobutyl terephthalate, dibutyl terephthalate, monoisobutyl phthalate, diisobutyl phthalate, monoamyl phthalate , cyamyl phthalate, monoisoamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, ethyl propyl phthalate, and the like.

In the present invention, any one of the various monoesters of aromatic dicarboxylic acids and diesters of aromatic dicarboxylic acids described above may be used alone, or two or more of them may be used in combination.

When comparing the aromatic dicarboxylic acid monoester and the aromatic dicarboxylic acid diester, the aromatic dicarboxylic acid diester is preferred.

Among the diesters of aromatic dicarboxylic acids, lower alkyl esters of phthalic acid (however, the lower alkyl group has 1 to 5 carbon atoms) are preferred, and dibutyl phthalate and diisobutyl phthalate are particularly preferred.

The silicon compound has the following formula: % formula % (wherein R1 represents an alkyl group, cycloalkyl group, or aryl group, xl represents a halogen atom such as chlorine or bromine, and m represents 0 to 3.0 represents a real number between ).

Specifically, the silicon compound is 5i(dL4
, CthO3iC13, (CH+0hSiC12, (C
H30) 3 Si0 sentence, C21 (5O3iC sentence 3, (C
2H3O)2SiG statement 2, (C2H50)3SiC intersection,
C3H70SiG sentence 3, (C3H70hSiC sentence 2, (
Examples include C:3H10hSiGi, which can be used alone or in combination.

Among the above, silicon tetrachloride (5i (Jj4)) is preferred.

As a specific example of the titanium tetrahalide, Tie Bun a
, TiBr4. Among them, titanium tetrachloride (TiC1s) is preferred.

Preparation of the solid catalyst component (A) Preferably, the solid catalyst component (A) is prepared in a two-step operation as described below.

That is, in the first step, the dialkoxymagnesium, the monoester of the aromatic dicarboxylic acid and/or the diester of the aromatic dicarboxylic acid, and the silicon compound are mixed in an inert solvent at a predetermined temperature and for a predetermined time. Allow the contact reaction to occur while stirring.

In this case, the amount of the aromatic dicarboxylic acid monoester and/or the aromatic dicarboxylic acid diester used is usually 0.01 to 1 times the mole of dialkoxymagnesium, preferably 0. ．．
05 to 0.5 times the mole.

The amount of the silicon compound to be used is usually 0.001 times or more, preferably 0.05 to 5 times the amount of dialkoxymagnesium.

If the amount of the silicon compound used is less than 0.01 times the mole or is too large, the polymerization activity of the catalyst will not be sufficiently improved, and the stereoregularity of the resulting olefin polymer will be insufficient. .

There is no particular restriction on the order in which the components are added, and the components may be added sequentially or simultaneously.

The solvent may be any solvent as long as it is inert with each component, such as aliphatic hydrocarbons, alicyclic hydrocarbons, etc. Specifically, pentane, hexane, n-hebutane,
Examples include cyclohexane.

Although the reaction using these solvents is a preferred embodiment of the present invention, it is also possible to carry out the reaction without a solvent. In this case, for example, the components may be directly mechanically mixed using a ball mill or the like and reacted.

The temperature of the reaction is usually -10 to 150°C, preferably 20 to 120°C, which is efficient, and the resulting catalyst has high polymerization activity.

Furthermore, since the reaction time depends on the reaction temperature, it may be appropriately selected depending on the reaction temperature.

In the second stage, the solid material obtained in the first stage, either washed or unwashed, is reacted with titanium tetrahalide.

The second step of the method of the present invention is carried out in the order described above, but usually in the liquid phase of the titanium tetrahalide compound or in an inert solvent such as pentane, hexane, n-hebutane, cyclohexane, etc. The reaction temperature is 20 to 200°C, preferably 50 to 150°C, and the reaction time is 5 minutes to 10 hours, preferably 30 minutes to 5 hours.

The amount of titanium tetrahalide used is 1 to 100 times the mole of magnesium in the first step, preferably 10
~100 times the molar amount.

In the present invention, the solid product obtained by the second-stage reaction is washed with an inert hydrocarbon such as pentane, hexane, cyclohexane, n-hebutane, etc. as necessary, and the solid product after washing is α -Used as a solid catalyst component (A) of an olefin polymerization catalyst.

For example, in the case of liquid phase polymerization, the amount of the solid catalyst component (A) used is 0.00 in terms of (A) ji in terms of titanium atoms.
1-10 mmoi/l, preferably O, QO5-5
IllOsL/sLte is there.

About the organoaluminum compound (B) The organoaluminum compounds include trimethylaluminum, triethylaluminum, triisopropylaluminum,
Trialkylaluminum compounds such as triisobutylaluminum and trioctylaluminum, and dialkylaluminum monohalides such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, diisobutylaluminum monochloride, and dioctylaluminum monochloride are suitable; Mixtures of these can also be used.

In the present invention, one of the various organoaluminum compounds described above may be used alone, or two or more thereof may be used in combination.

Among the various organoaluminum compounds described above, trialkylaluminum having a lower alkyl group having 1 to 5 carbon atoms is preferred, and trimethylaluminum, triethylaluminum, tribupylaluminum, tributylaluminium, and the like are particularly preferred.

The amount of the organoaluminum compound used is usually 1 to 1,000 titanium atoms in the solid catalyst component (A).
(molar ratio), preferably 10 to 500 (molar ratio).

About the electron donating compound (C) The electron donating compound is an organic compound containing oxygen, nitrogen, phosphorus, or sulfur, and specific examples thereof include amines, amides, ketones, and nitriles. , phosphines, phosphoramides, esters, ethers, thioethers, thioesters, acid anhydrides, acid halides, acid amides, aldehydes, organic acids, organic silane compounds having a 5i-0-G bond, etc. can be mentioned.

More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and P-oxybenzoic acid: succinic anhydride;
Acid anhydrides such as benzoic anhydride, P-)ruylic anhydride =
Ketones with 3 to 15 carbon atoms, such as a7tone, methyl ale ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone: 2 to 15 carbon atoms, such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, etc. aldehydes; methyl formate, methyl acetate,
Ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl toluate Ethyl benzoate, methyl anisate,
Ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl 0-chlorobenzoate, ethyl naphthoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, di-n phthalate
-butyl, di-1so-butyl phthalate, dihebutyl phthalate, dicyclohexyl phthalate, etc. having 2 to 1 carbon atoms
8 esters; Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride, toluic acid chloride, anisyl chloride: methyl ether, ethyl ether, isopropyl ether, t-butyl methyl ether, t-butyl ethyl ether , n-butyl ether,
Ethers with 2 to 20 carbon atoms such as amyl ether, tetrahydrofuran, anisole, diphenyl ether, and ethylene glycol butyl ether; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; Tributylamine, N,N-dimethylpiperazine, and Examples include amines such as livenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile, and tolnitrile, tetramethylurea, nitrobenzene, and lithium butyrate.

Furthermore, examples of the organosilicon compound having the Si-〇-11: bond include alkoxysilane and aryloxysilane.

Examples of this include - tubular formula: % formula %:) (wherein R2 represents an alkyl group, cycloalkyl group, aryl group, alkenyl group, haloalkyl group, aminoalkyl group, or halogen atom, and R3 represents an alkyl group, an aminoalkyl group, or a halogen atom). group, cycloalkyl group, aryl group, alkenyl group, or alkoxyalkyl group. Also, W is 0≦W≦3.However, W (g) R2 and (4-w) OR3 are each the same. It may be different or different. )
Examples include silicic acid esters represented by:

Other examples include siloxanes having an OR3 group or silyl esters of carboxylic acids. Furthermore, as another example, a silicon compound having no Si-0-C bond and an organosilicon compound having an O-C bond may be reacted in advance or reacted during the polymerization of α-olefin to form a Si-0-C bond. Examples include those converted to organosilicon compounds having a bond, such as a combination of 5i(44 and alcohol).

Specific examples of the organosilicon compounds having the 5i-0-C bond include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, and diphenyljetoxysilane. Toxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chloro Triethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriacetoxysilane, dimethyltetraethoxy Examples include disiloxane.

Among the various electron-donating compounds (C), preferred are esters, ethers, ketones, acid anhydrides, organic silane compounds having a 5i-0-C bond, and the like.

In particular, di-n-butyl phthalate, di-1so- phthalate,
Use of phthalate esters such as butyl, diheptyl phthalate, and dicyclohexyl phthalate in combination with ethers such as E-butyl methyl ether and t-butyl ethyl ether, and alkyl esters of aromatic carboxylic acids such as benzoic acid and p-methoxy Benzoic acid, p-ethoxybenzoic acid,
C1-4 alkyl esters of aromatic carboxylic acids such as toluic acid, trialkoxysilanes, etc. are preferred; aromatic ketones such as benzoquinone; aromatic carboxylic acid anhydrides such as benzoic anhydride; and ethylene glycol butyl ether. Ethers such as are also preferred.

The amount of the electron donating compound (C) used is 1 to 500 (mole ratio), preferably 5 to 200 (mole ratio), based on the titanium atoms of the solid catalyst component (A).

Regarding olefins, there are no particular limitations on the olefins that can be used in the method of the present invention, but they are usually expressed by the following formula: % (wherein R4 represents hydrogen or an alkyl group having 1 to 6 carbon atoms). For example, linear monoolefins such as ethylene, propylene, butene-1, hexene-1, and octene-1, and branched monoolefins such as 4-methylpentene-1 are mentioned.

These olefins may be used alone, or two or more olefins may be used in combination.

Among the above, ethylene and propylene are particularly preferred.

Furthermore, in the method of the present invention, dienes such as butadiene and various other dienes can be used.

Production of olefin polymer In the present invention, when polymerizing olefins, especially α-olefins, a dispersion of a solid catalyst component as component (A) and an organoaluminum compound as component (B) are added to the reaction system. , an olefin is introduced into this system using an electron-donating compound as component (C) as a catalyst.

There are no particular restrictions on the polymerization method and conditions, and slurry polymerization using an inert hydrocarbon solvent, liquid phase polymerization without a solvent,
Either gas phase polymerization or the like is possible, and both continuous polymerization and discontinuous polymerization are possible. Furthermore, the polymerization reaction may be carried out in one stage or in multiple stages of two or more stages.

In a multi-stage polymerization reaction, for example, a two-stage polymerization reaction, in the first stage, for example, a polymerization reaction of, for example, propylene is carried out in the presence of the catalyst components (A), (B) and (C) to produce crystalline polypropylene, In the second stage, the catalyst component (A) is added in the presence of the crystalline propylene, with or without removing the unreacted propylene subjected to the first stage polymerization.
Ethylene and propylene are copolymerized in the presence of (B) and (C).

In the above reaction, the olefin pressure is normal pressure to 50 kg/c
112, and the reaction temperature is 0 to 200°C, preferably 3ON100°C.

The reaction time is 5 minutes to 10 hours, preferably 30 minutes to 5 hours.

Molecular weight adjustment during polymerization can be carried out by known means, such as hydrogen.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

(Example 1) ■ Preparation of solid catalyst component (A) Dehydrated n-hebutane 6 in a 500 mM fourth flask
0 layer, 4.5 g of jetoxymagnesium, and 1.2 layer of di-n-butyl phthalate were added, and after stirring at room temperature,
Add 1.5 layers of silicon tetrachloride, raise the temperature, and boil under reflux for 30 minutes.
Allowed to react for minutes.

100 mM of titanium tetrachloride was added to this, and the reaction was carried out at 110° C. for 2 hours. Thereafter, washing was performed with n-hebutane, 100 layers of titanium tetrachloride was added, and the reaction was carried out at 110°C for 2 hours, followed by thorough washing with n-hedane to remove the solid catalyst component (A). Obtained. The titanium content per gram of catalyst was 25+++g, and the di-n-butyl phthalate content per gram of catalyst was 143i+H.

■Manufacture of olefin polymer 400 tJL of n-hebutane was put into a stainless steel autoclave, and then 0.1+u+o of tert-butyl methyl ether (triisobutylaluminum, component (B))
u and dicyclohexyl phthalate 0.088m 0
Then, 0.0025 mol of the solid catalyst component (A) in terms of titanium atoms was added, and the hydrogen pressure was 0.2 kg/
Polymerization was carried out at 70° C. for 2 hours while maintaining the propylene pressure at 7.0 kg/c2. The yield of polypropylene was 532 kg per tg of titanium, and the boiling hebutane extraction residue (1.1.) was 97.8% (Example 2) In the production of the olefin polymer of Example 1■, Similar polymerization was carried out for 2 hours using triethylaluminum instead of triisobutylaluminum and diphenyldimethoxysilane having a layer size of 0.025 as the electron donating compound (C). As a result, the yield of polypropylene was 723 kg per Ig of titanium, and the yield was 1.1. is 88
．． It was 2%. In addition, when the polymerization time was set to 3 hours,
The yield of polypropylene per tg of titanium is 1332k
g, 1.1. was 98.0%. (Example 3) ■Preparation of solid catalyst component In the preparation of the solid catalyst component in Example 1■, the same procedure was followed except that diisobutyl phthalate was used instead of di-n-butyl phthalate. As a result of the preparation, the titanium content per gram of catalyst was 22 g, and the content of diisobutyl phthalate per gram of catalyst was 128 g.

■Production of olefin polymer When polymerization was carried out under the same conditions as in Example 2, titanium 1
The yield of polypropylene per g is 885 kg,
1.1. was 87.9%.

(Comparative Example 1) ■Preparation of solid catalyst component In the preparation of the solid catalyst component in Example 1■, di-n-butyl phthalate was replaced with ethylbenzony) 1.2+
A solid catalyst component was prepared by performing the same operation except that wu was used. The titanium content per gram of catalyst is 32 mg, and the content of ethyl benzoate per gram of catalyst is 1.
It was 40 mg.

■Production of olefin polymer In the production of the olefin polymer in Example 1■, (C)
p-methyltorny in place of tert-butyl methyl ether and dicyclohexyl phthalate)
The same operation was carried out except that 0.27 ml was used, and as a result of polymerization for 2 hours, the yield of polypropylene was 212 kg per Ig of titanium, and the yield was 1.1. was 96.5%. In addition, when the polymerization time was set to 3 hours, titanium 1
The yield of polypropylene per gram is only 252 kg, which is 1.1. It also decreased to 94.8%.

(Example 4) A propylene-ethylene copolymer was produced in the following manner using the solid catalyst component (A) obtained in the same manner as in the preparation of the solid catalyst component (A) in Example 1. I did it.

(2) Production of propylene-ethylene copolymer After purging an autoclave with an internal volume of 5 liters sufficiently with nitrogen gas, 20 g of dried polypropylene powder was charged. Thereafter, 0.1 ml of triethylaluminum toxyphenylsilane as component (B) and 0.1 mmol of solid catalyst component (A) in terms of titanium atoms were charged into the crepe. Hydrogen and propylene were introduced, and the temperature and pressure were increased to 70° C. and 20 kg/c+w2.

The polymerization reaction was carried out under these conditions for 2 hours. The intrinsic viscosity [η] of the obtained propylene homopolymer was 162 d/g.

After the polymerization was complete, a gas mixture of ethylene and propylene and hydrogen were introduced, and the second stage polymerization was carried out at 55°C for 2 hours while maintaining the mixed gas pressure at 18 J/cm2. The reaction was carried out. The intrinsic viscosity [η] of the obtained propylene-ethylene copolymer was 4-oa9. /g, the ethylene content is 40% by weight, and the amount produced is 16
% by weight.

After the polymerization was completed, unreacted gas was removed to obtain a propylene polymer composition.

Predetermined additives were added to the obtained propylene polymer composition, mixed, and granulated using an extruder. Test pieces were prepared and their physical properties were evaluated. Flexural modulus is 17,000kg/cm
2.Izotsu impact strength is 3.0kg-Crm/c (
-20°C, with a notch).

[Effects of the Invention] As explained above, according to the production method of the present invention, the polymerization activity of the catalyst is high, and the polymerization activity does not decrease over time, making it possible to efficiently obtain an olefin polymer. Therefore, the catalyst removal step and the polymer washing step can be simplified or omitted. Furthermore, the obtained olefin polymer has various advantages such as high stereoregularity and less contamination with catalyst residue.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram showing the procedure for preparing a catalyst in the present invention. Procedural amendment February 3, 1989

Claims (1)

[Claims] (1) a) dialkoxymagnesium, b) monoester of aromatic dicarboxylic acid and/or diester of aromatic dicarboxylic acid, c) following formula: Si(
OR^1) __m d) A reaction product obtained by reacting a silicon compound represented by (representing a real number between 0) and d) titanium tetrahalide (A)
A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of a catalyst obtained from a solid catalyst component, (B) an organoaluminum compound, and (C) an electron-donating compound.